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The title compound, C10H11NO2S, was crystallized from solution as a by-product during the synthesis of ethyl dimethyl oxamate. It should be noted that Nair & Sheeba [J. Org. Chem. (1999). 64, 6898-6900] also synthesized an oxamate as a by-product during the transformation of acetoacetamides to cyclic compounds that was modified later to the synthesis of oxamates as primary products. NMR analysis of the compound did not provide a good basis for structural elucidation as it gave no indication of the presence of any heteroatom directly attached to the phenyl ring. X-ray single-crystal analysis revealed the direct attachment of an S atom to the ipso-carbon of the phenyl ring. The resultant structure is a thiooxamate. The two carbonyl groups are not coplanar.
Supporting information
CCDC reference: 642898
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- R factor = 0.029
- wR factor = 0.073
- Data-to-parameter ratio = 13.8
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 400 Deg.
PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C7 - C8 ... 1.54 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
S-Phenyl
N,
N'-dimethyl-
13C
2-thiooxamate
top
Crystal data top
C10H11NO2S | Z = 2 |
Mr = 209.26 | F(000) = 220 |
Triclinic, P1 | Dx = 1.395 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.8925 (16) Å | Cell parameters from 3343 reflections |
b = 7.950 (2) Å | θ = 2.7–32.2° |
c = 11.332 (3) Å | µ = 0.30 mm−1 |
α = 73.332 (4)° | T = 100 K |
β = 86.321 (4)° | Plate, colourless |
γ = 78.345 (4)° | 0.30 × 0.30 × 0.10 mm |
V = 498.1 (2) Å3 | |
Data collection top
Bruker SMART APEX II CCD area-detector diffractometer | 2360 independent reflections |
Radiation source: fine-focus sealed tube | 2006 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
φ and ω scans | θmax = 28.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −7→7 |
Tmin = 0.920, Tmax = 0.970 | k = −10→10 |
6584 measured reflections | l = −14→14 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | All H-atom parameters refined |
S = 1.02 | w = 1/[σ2(Fo2) + (0.04P)2 + 0.07P] where P = (Fo2 + 2Fc2)/3 |
2360 reflections | (Δ/σ)max = 0.020 |
171 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
Special details top
Experimental. 13C NMR: δ 14.001 (CH3), 34.054, 37.132, (d, J = 232.26 Hz, N(CH3)2),
62.040 (OCH2), 161.792 (13C=O). 1H NMR: δ = 1.349, 1.373, 1.397, (t,
J=7.18 Hz, CH3), 2.989, 2.999, 3.024, 3.03 (m, J = 7.56 Hz, N(CH3)2),
4.308, 4.332, 4.356, 4.380 (m, J = 7.23 Hz, OCH2). |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.24596 (5) | 0.06140 (4) | 0.62909 (3) | 0.02373 (10) | |
O1 | 0.32567 (17) | −0.11553 (11) | 0.86458 (8) | 0.0285 (2) | |
O2 | 0.59622 (16) | 0.21488 (13) | 0.75023 (10) | 0.0342 (2) | |
N1 | 0.29235 (17) | 0.26549 (12) | 0.87831 (9) | 0.0194 (2) | |
C1 | 0.1360 (2) | −0.13507 (15) | 0.64018 (10) | 0.0190 (2) | |
C2 | −0.0764 (2) | −0.15378 (16) | 0.69700 (11) | 0.0218 (2) | |
H2 | −0.156 (3) | −0.060 (2) | 0.7251 (16) | 0.038 (4)* | |
C3 | −0.1629 (2) | −0.30758 (17) | 0.70555 (12) | 0.0252 (3) | |
H3 | −0.308 (3) | −0.317 (2) | 0.7446 (15) | 0.038 (4)* | |
C4 | −0.0391 (2) | −0.43927 (17) | 0.65622 (11) | 0.0257 (3) | |
H4 | −0.101 (3) | −0.545 (2) | 0.6633 (14) | 0.033 (4)* | |
C5 | 0.1709 (2) | −0.41762 (16) | 0.59712 (12) | 0.0250 (3) | |
H5 | 0.257 (3) | −0.508 (2) | 0.5635 (15) | 0.037 (4)* | |
C6 | 0.2606 (2) | −0.26525 (17) | 0.58865 (11) | 0.0228 (2) | |
H6 | 0.401 (3) | −0.252 (2) | 0.5503 (15) | 0.031 (4)* | |
C7 | 0.32671 (19) | 0.02062 (15) | 0.78370 (11) | 0.0188 (2) | |
C8 | 0.4155 (2) | 0.18000 (15) | 0.80300 (11) | 0.0202 (2) | |
C9 | 0.0745 (2) | 0.22520 (19) | 0.93659 (13) | 0.0275 (3) | |
H9A | 0.099 (3) | 0.157 (2) | 1.0190 (18) | 0.046 (5)* | |
H9B | −0.024 (3) | 0.339 (2) | 0.9314 (16) | 0.041 (4)* | |
H9C | 0.005 (3) | 0.160 (2) | 0.8935 (16) | 0.040 (4)* | |
C10 | 0.3749 (2) | 0.40934 (17) | 0.90732 (13) | 0.0240 (3) | |
H10A | 0.517 (3) | 0.411 (2) | 0.8802 (17) | 0.050 (5)* | |
H10B | 0.277 (3) | 0.522 (2) | 0.8710 (15) | 0.035 (4)* | |
H10C | 0.381 (3) | 0.384 (2) | 0.9966 (16) | 0.038 (4)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.03238 (18) | 0.02088 (16) | 0.01994 (16) | −0.01229 (12) | −0.00215 (11) | −0.00352 (11) |
O1 | 0.0413 (5) | 0.0206 (4) | 0.0247 (5) | −0.0100 (4) | −0.0068 (4) | −0.0041 (3) |
O2 | 0.0262 (5) | 0.0319 (5) | 0.0534 (6) | −0.0139 (4) | 0.0138 (4) | −0.0235 (5) |
N1 | 0.0213 (5) | 0.0170 (5) | 0.0227 (5) | −0.0067 (4) | −0.0010 (4) | −0.0076 (4) |
C1 | 0.0231 (6) | 0.0180 (5) | 0.0172 (5) | −0.0064 (4) | −0.0037 (4) | −0.0042 (4) |
C2 | 0.0220 (6) | 0.0215 (6) | 0.0230 (6) | −0.0031 (5) | −0.0019 (5) | −0.0081 (5) |
C3 | 0.0227 (6) | 0.0302 (6) | 0.0240 (6) | −0.0109 (5) | −0.0032 (5) | −0.0049 (5) |
C4 | 0.0344 (7) | 0.0211 (6) | 0.0231 (6) | −0.0092 (5) | −0.0108 (5) | −0.0034 (5) |
C5 | 0.0322 (6) | 0.0211 (6) | 0.0232 (6) | −0.0009 (5) | −0.0065 (5) | −0.0098 (5) |
C6 | 0.0226 (6) | 0.0268 (6) | 0.0203 (6) | −0.0048 (5) | −0.0007 (5) | −0.0086 (5) |
C7 | 0.0179 (5) | 0.0182 (5) | 0.0224 (6) | −0.0045 (4) | 0.0002 (4) | −0.0085 (4) |
C8 | 0.0188 (5) | 0.0176 (5) | 0.0254 (6) | −0.0043 (4) | −0.0016 (4) | −0.0073 (4) |
C9 | 0.0294 (7) | 0.0285 (7) | 0.0298 (7) | −0.0127 (5) | 0.0081 (5) | −0.0130 (6) |
C10 | 0.0270 (7) | 0.0207 (6) | 0.0296 (7) | −0.0086 (5) | −0.0031 (5) | −0.0121 (5) |
Geometric parameters (Å, º) top
S1—C7 | 1.7663 (13) | C4—C5 | 1.387 (2) |
S1—C1 | 1.7781 (12) | C4—H4 | 0.965 (16) |
O1—C7 | 1.2019 (14) | C5—C6 | 1.3932 (17) |
O2—C8 | 1.2289 (15) | C5—H5 | 0.953 (16) |
N1—C8 | 1.3308 (15) | C6—H6 | 0.918 (16) |
N1—C10 | 1.4538 (14) | C7—C8 | 1.5392 (15) |
N1—C9 | 1.4567 (16) | C9—H9A | 0.940 (19) |
C1—C2 | 1.3856 (17) | C9—H9B | 0.961 (17) |
C1—C6 | 1.3914 (17) | C9—H9C | 0.964 (17) |
C2—C3 | 1.3935 (17) | C10—H10A | 0.88 (2) |
C2—H2 | 0.921 (18) | C10—H10B | 0.958 (17) |
C3—C4 | 1.3840 (19) | C10—H10C | 0.975 (18) |
C3—H3 | 0.942 (17) | | |
| | | |
C7—S1—C1 | 100.18 (5) | C1—C6—H6 | 120.9 (10) |
C8—N1—C10 | 119.72 (10) | C5—C6—H6 | 120.1 (10) |
C8—N1—C9 | 124.49 (10) | O1—C7—C8 | 122.52 (10) |
C10—N1—C9 | 115.79 (10) | O1—C7—S1 | 126.02 (9) |
C2—C1—C6 | 120.91 (11) | C8—C7—S1 | 111.37 (8) |
C2—C1—S1 | 119.37 (9) | O2—C8—N1 | 125.58 (11) |
C6—C1—S1 | 119.70 (9) | O2—C8—C7 | 117.54 (10) |
C1—C2—C3 | 119.40 (11) | N1—C8—C7 | 116.85 (10) |
C1—C2—H2 | 117.2 (10) | N1—C9—H9A | 110.4 (11) |
C3—C2—H2 | 123.3 (10) | N1—C9—H9B | 105.5 (10) |
C4—C3—C2 | 120.25 (12) | H9A—C9—H9B | 111.1 (15) |
C4—C3—H3 | 121.9 (10) | N1—C9—H9C | 110.8 (10) |
C2—C3—H3 | 117.9 (10) | H9A—C9—H9C | 109.0 (14) |
C3—C4—C5 | 119.95 (11) | H9B—C9—H9C | 110.0 (14) |
C3—C4—H4 | 119.3 (9) | N1—C10—H10A | 109.6 (12) |
C5—C4—H4 | 120.8 (9) | N1—C10—H10B | 110.5 (10) |
C4—C5—C6 | 120.48 (12) | H10A—C10—H10B | 110.0 (15) |
C4—C5—H5 | 120.3 (10) | N1—C10—H10C | 108.5 (9) |
C6—C5—H5 | 119.2 (10) | H10A—C10—H10C | 106.4 (15) |
C1—C6—C5 | 118.98 (12) | H10B—C10—H10C | 111.7 (13) |
| | | |
C7—S1—C1—C2 | 73.25 (10) | C1—S1—C7—O1 | 7.23 (12) |
C7—S1—C1—C6 | −108.64 (10) | C1—S1—C7—C8 | −176.21 (8) |
C6—C1—C2—C3 | 1.81 (18) | C10—N1—C8—O2 | −2.38 (19) |
S1—C1—C2—C3 | 179.90 (9) | C9—N1—C8—O2 | 177.89 (12) |
C1—C2—C3—C4 | −0.86 (18) | C10—N1—C8—C7 | 175.79 (10) |
C2—C3—C4—C5 | −0.55 (18) | C9—N1—C8—C7 | −3.94 (17) |
C3—C4—C5—C6 | 1.04 (18) | O1—C7—C8—O2 | 111.20 (14) |
C2—C1—C6—C5 | −1.32 (18) | S1—C7—C8—O2 | −65.49 (13) |
S1—C1—C6—C5 | −179.40 (9) | O1—C7—C8—N1 | −67.12 (15) |
C4—C5—C6—C1 | −0.12 (18) | S1—C7—C8—N1 | 116.19 (10) |
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